JPS6366803B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to hair treatment compositions containing surface-active cyclic and/or linear polysiloxanes. The surface-active polysiloxanes according to the invention have surprising properties, in particular amphophilicity, ie an affinity for both water and organic media, giving them a strong surface activity. This polysiloxane also differs from conventional surfactants, which contain one lipophilic chain per molecule. As is well known, when conventional surfactants are dissolved in water, above a concentration limit called the "critical micelle concentration," they develop a set of properties that are highly effective for a number of different purposes. In particular at concentrations at least equal to this limit value, these surfactants dissolve organic substances (eg fat-soluble dyes and hydrocarbons) in water. The compounds according to the invention have solubilizing properties at very low concentrations, often well below the critical micelle concentration of surfactants with corresponding length of lipophilic chains. This is an important advantage for surfactants used in pharmaceutical or cosmetic compositions where it is desired to minimize the amount of surfactant used so as not to harm the main components of the composition. becomes. Furthermore, the compounds of the present invention are less irritating to the skin and mucous membranes (especially the mucous membranes of the eyes) and/or cause less denaturation of proteins than surfactants having one lipophilic chain or a corresponding functional group per molecule. The degree to which it does so is small. The surface active polysiloxane of the present invention can be represented by the following general formula. In the formula, A is a hydrophilic unit bonded to the chain through a decamethylene group -( _CH2 ) _10- constituting the lipophilic moiety, and x represents an integer from 3 to 10 (preferably 3 to 6). Polysiloxanes of formula () are generally cyclic. However, the present invention also encompasses linear polysiloxanes of formula (). The cyclic and/or linear polysiloxanes can take the form of either a single compound or a mixture of compounds. The hydrophilic unit A may be cationic, zwitterionic, anionic or nonionic. A is a group consisting of one or more (same or different) amine, amine oxide, ammonium, ammonioalkyl carboxylate, ammonioalkyl sulfonate, amide, sulfonamide, ether, thioether, sulfoxide, hydroxyl, ester, or acid group. can include. A typical hydrophilic unit A is one of the following groups: (stomach) (However, R ₁ is [-CH ₂ -CH ₂ -O]- _o H,
n is an integer from 1 to 10, and u is 0 or 1), (b) (However, V is an anion of an organic or inorganic acid, R ₁ is as defined in (a), and u is 0 or 1), (c) -CONH-(CH ₂ ) _n - B (However, m is 2 or 3, B is a group

[expression] or

[Formula] (u is 0 or 1, V is an anion of an organic acid or inorganic acid), (d) (However, u and w are the same or different and are 0 or 1, M represents a hydrogen atom, an ammonium group, or an alkali metal), (e) CH ₂ -O-SO ₃ M (However, M is (d) ), (f) (However, p and q may be the same or different and indicate a positive number up to 0 or 10, but both p and q are not 0.
Y represents hydroxypropylene group, Z represents OH
or

[Formula] (where u is 0 or 1, and M represents a hydrogen atom, an ammonium group, or an alkali metal). As shown in formula (F), [-Y-O]- and

[Formula] The most common distribution of units is block distribution. However, a random distribution is also possible, especially if Y is a hydroxypropylene group. The compound of formula () can be produced by a method consisting of the following several steps. (1) React the acetate ester of undecylenyl alcohol or the methyl or ethyl ester of undecylenic acid with methyldichlorosilane. (2) Remove water by controlled hydrolysis and polymerization. (3) Next, one or more reactions are performed to introduce the desired hydrophilic unit A. The reaction between the above ester and methyldichlorosilane is carried out in an autoclave at, for example, 110°C to 130°C.
The reaction can be carried out at a temperature of 1,000 ml, preferably in the presence of hexachloroplatinic acid (generally in the form of a methanol solution). This reaction can be diagrammed as follows. In the formula, R ₃ is

【formula】

[Formula] or

Represents [formula]. As a result of controlled hydrolysis (preferably carried out in the presence of sodium or potassium hydroxide), chlorine atoms are replaced by hydroxyl groups. The resulting product is dehydrated and polymerized to give a cyclic or linear compound. The resulting compounds are generally cyclic. The hydrolysis and polymerization reactions are generally carried out in water and an inert solvent (eg tetrahydrofuran or dioxane) at temperatures from 0 to 80°C (preferably from 0 to 40°C, preferably from 0 to 10°C). Depending on whether the acetate ester of undecylenyl alcohol or the methyl or ethyl ester of undecylenic acid is used as starting material, the resulting intermediate has the formula () or ().

【formula】

[Formula] In the formula, x represents an integer from 3 to 10 (preferably 3 to 6), and R represents CH ₃ or C ₂ H ₅ . When the compounds of formulas () and () are saponified,
They become compounds of formulas (a) and (a), respectively.

【formula】

[Formula] In the formula, x shall be defined above. The present invention also provides intermediates of the formula and mixtures thereof produced before or after saponification. In the formula, R ₄ is −CH ₂ OCOCH ₃ , −CH ₂ OH, −
It represents COOCH ₃ or -COOC ₂ H ₅ , and x represents an integer from 3 to 10 (preferably from 3 to 6). The present invention also provides a method for producing a surface-active polysiloxane comprising: (1) Reaction of acetate ester of undecylenyl alcohol or methyl or ethyl ester of undecylenic acid with methyldichlorosilane under the conditions specified above. (2) Substitution of the above chlorine atom with a hydroxyl group. (3) Of the formed -CH ₂ -OCOCH ₃ , -COOCH ₃ or -COOC ₂ H ₅ group, (a), (b), (c), as defined above,
Substitution of (d), (e) and (f) with hydrophilic groups. Compounds of type (a) [i.e., compounds of formula () where A represents group (a)] are the compounds of formula (2) in which dimethylamine or methylethanolamine is converted into an intermediate (
Chlorinated or brominated derivatives of a) [This derivative is obtained by reacting a compound of formula (a) with thionyl chloride or hydrobromic acid, respectively]
or with the mesylate or tosylate of intermediate (a), which is obtained by mesylation or tosylation, respectively. In other words, compounds of type (a) can be prepared by reacting dimethylamine or methylethanolamine with an intermediate of formula (). In the formula, x represents an integer from 3 to 10 (preferably 3 to 6), and R ₅ is -CH ₂ Cl, -CH ₂ Br,
-CH ₂ -O-SO ₂ -CH ₃ or -CH ₂ -O-SO ₂ -
Represents C ₆ H ₄ −CH ₃ . The condensation of the amine can be carried out under atmospheric pressure or in an autoclave, suitably at a temperature of 20°C to 160°C, and optionally in the presence of an alkaline compound (for example sodium methylate). When using methylethanolamine, the resulting compound can be oxyethylated as desired. It is also possible to oxidize the amine group (eg with hydrogen peroxide or a peracid) to convert it to an amine oxide. Compounds of type (b) [i.e., compounds of formula () where A represents a (b) group] are compound (i)
by salting with a mineral acid or an organic acid (preferably any of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid, acetic acid, glycolic acid, lactic acid, tartaric acid, methanesulfonic acid and para-toluenesulfonic acid). can get. Compounds of type (c) [i.e., compounds of formula () where A represents a group (c)] are prepared by converting the intermediate of the following formula () into a suitable primary/tertiary compound when w is 0. It can be produced by condensation with a diamine (eg dimethylaminoethylamine or dimethylaminopropylamine). In the formula, R represents CH ₃ or C ₂ H ₅ , and x
represents an integer from 3 to 10 (preferably 3 to 6). When w is 1, compounds of type (c) can be obtained by condensing a suitable primary/tertiary diamine with an intermediate of the following formula (). In the formula, R represents CH ₃ or C ₂ H ₅ and x is as defined above. Intermediate () can be obtained by reacting methyl thioglycolate or ethyl thioglycolate with an intermediate of the following formula (). In the formula, x is as defined above, and R ₅ is -CH ₂ Cl, -CH ₂ Br, -CH ₂ -O-SO ₂ -CH ₃ or -CH ₂ -O-SO ₂ -C ₆ H ₄ -Represents CH ₃ . Intermediates () are R ₅ -CH ₂ Cl, -CH ₂ Br, -
CH ₂ -O-SO ₂ CH ₃ or -CH ₂ -O-SO ₂ -C ₆ H ₄
Depending on which of -CH ₃ is represented, the intermediate (a) is thionyl chloride, hydrobromic acid, or
It can be produced by reacting with mesyl chloride or tosyl chloride. Condensation of primary/tertiary diamines starts from 20°C.
It is appropriate to carry out the reaction at a temperature of 160°C. The amine group and the sulfur atom (when w=1),
For example, using hydrogen peroxide or peracid,
By oxidation at temperatures of 0.degree. C., they can be made into amine oxides and sulfoxides, respectively. Furthermore, the tertiary amine or amine oxide group of the aminoamide thus obtained can then be salified with a mineral or organic acid [as described for compounds of type (b)], and u=0 In this case, it can also be alkylated using an alkylating agent. Compounds of type (d) [i.e., compounds of formula () where A represents group (d)], when w is 0, are prepared by mixing the intermediate () of the following formula with ammonia or an alkali metal hydroxide. When M is hydrogen, it can be produced by suitably acidifying the hydrogen. In the formula, R represents CH ₃ or C ₂ H ₅ . When w is 1, compounds of type (2) can be prepared by saponifying the intermediate () with an alkali metal hydroxide or ammonia and then acidifying it appropriately, removing the sulfur atoms present. For example, it is also possible to oxidize with hydrogen peroxide or peracid to form a sulfoxide. Compounds of type (e) [i.e., compounds of formula () where A represents a (e) group] are intermediates (
It can be produced by reacting a) with chlorosulfonic acid and, if deemed appropriate, neutralizing with ammonia or an alkali metal hydroxide. These reactions can be carried out without a solvent or in the presence of a solvent (eg chloroform, benzene, toluene or ether); temperatures from 0°C to 80°C are suitable. Compounds of type (f) [i.e. compounds of formula () where A represents a (f) group] can be prepared in the presence of an acidic catalyst (e.g. boron trifluoride or tin tetrachloride) or in the presence of a basic catalyst (e.g. sodium Reagents containing epoxide groups and intermediates (a) in the presence of methylates, sodium ethylates, potassium methylates or potassium ethylates; however, basic catalysts must not be used in the polyaddition of epihalogenhydrins). It is obtained by a polyaddition reaction consisting of one or more steps. Epoxides that can be used include ethylene oxide,
Included are tertiary butyl glycidyl ether (TBGE) and/or epihalogenhydrins (eg epichlorohydrin or epibromohydrin) and mixtures thereof. Polyaddition reactions are generally carried out in a continuous operation, but
When using TBGE and epihalogenhydrin, these two reagents can be added simultaneously or as a mixture. In the presence of strong acids (e.g. sulfocarboxylic acids),
For example, by heating from 50°C to 120°C, the tertiary butoxy protecting group can be substituted with a hydroxyl group. The halogen atom in the oligomer obtained by reaction with epihalogenhydrin can be a hydroxyl group, thiohydroxyethyl, thiodihydroxypropyl, thioglycolate, amine, ammonium, ammonioacetate, ammoniopropionate, ammoniopropanesulfonate or sulfonate. can be replaced by Substitution of a halogen atom with a hydroxyl group can be performed as follows. Reaction with an alkali metal salt of a carboxylic acid (sodium acetate or potassium acetate is suitable) in a suitable solvent (preferably a glycol or glycol derivative) at a temperature of 150°C to 260°C. The resulting acetate ester is then subjected to saponification, hydrolysis using sodium hydroxide or potassium hydroxide, or alcoholysis with a lower alcohol (preferably methanol or ethanol) using a basic catalyst (sodium methylate, sodium ethylate, potassium hydroxide, etc.). methylate or potassium ethylate are preferred). The hydroxyl groups can then be replaced with sulfate or sulfoacetate groups by esterification using chlorosulfonic acid or sulfoacetic acid. Substitution of halogen atoms with thiohydroxyethyl, thiodihydroxypropyl or thioglycolate groups can be carried out, for example, at 20°C to 150°C with alkaline compounds (sodium hydroxide, sodium methylate or sodium ethylate, or potassium hydroxide, potassium methyl The reaction can be carried out by reaction with thioethanol, thioglycerol, methylthioglycolate or ethylthioglycolate in the presence of a suitable solvent (preferably ethylate or potassium ethylate). Substitution of a halogen atom with an amine group can be
This can be done in the same way as in case (a). The amine groups and sulfur atoms present can be oxidized to amine oxide and sulfoxide groups using hydrogen peroxide or organic peracids. Furthermore, an amine or amine oxide group can be added to the compound.
It can also be converted into an ammonium group by chlorination and/or alkylation in the same manner as described for (b). The substitution of a halogen atom with an ammoniopropanesulfonate, ammonioacetate or ammoniopropionate group can be carried out in two steps. In the first step, the halogen is replaced by an amine group, and in the second step, the formula Hal-CH ₂ -CH ₂ -
CH ₂ −SO ₃ H (Hal is chlorine or bromine)
or the sodium or potassium salts of this acid, or preferably propane-sultone (to obtain the propane sulfonate group), or chloroacetic acid, chloropropionic acid, methyl chloroacetate, ethyl chloroacetate, chloropropionic acid. Using methyl or ethyl chloropropionate, basic compounds (e.g. sodium methylate, sodium ethylate, sodium hydroxide,
potassium methylate, potassium ethylate, or potassium hydroxide), e.g. from 20°C.
The amine is alkylated to give ammonioacetate or ammoniopropionate groups at a temperature of 150°C. The substitution of halogen atoms by sulfonates can be carried out by heating in an autoclave with sodium sulfite in an aqueous solution or a mixture of water and a hydroxyl compound containing up to 6 carbon atoms (e.g. alcohol, glycol or alkoxyethanol). . In the last case, it is also possible to carry out the reaction directly with the tert-butoxy group. A compound of formula () containing an oxidizing nitrogen or sulfur atom is prepared by a conventional method using hydrogen peroxide or a peracid (e.g. peracetic acid or performic acid), generally from 10°C.
It can be converted to amine oxide or sulfoxide by oxidation at a temperature of 100°C. The surface-active polysiloxanes of formula () according to the invention are generally in the form of water-soluble or water-dispersible powders, pastes or oils. Among the water-insoluble compounds that can be solubilized by surface-active polysiloxanes of formula ()
Of particular note are dyes, fragrances and certain pharmaceutical products. Apart from solubilizing these products, surface-active polysiloxanes of formula () can solubilize or disperse inorganic or polar compounds in organic media or hydrophobic compounds in aqueous media. . The compounds of the invention can be used in various industries, especially in cosmetics and medicine, textiles, dyeing and pesticides. The present invention also provides compositions containing at least one surface-active polysiloxane of formula (). Among these compositions, at least 0.5×
10 ^-2 g/(or 0.5 x 10 ^-3 weight%) formula ()
Particular mention is made of cosmetic and pharmaceutical compositions containing surface-active polysiloxanes. Cosmetic compositions include compositions intended in particular for the care of the skin, nails and hair. Preferably, the hair-care composition is an aqueous composition which may also contain adjuvants conventionally used in compositions for the treatment of keratinous substances. The most striking effects of the compounds of the invention can be seen in cosmetic applications, especially when used in hair treatments. These cosmetic compositions can take the form of, for example, aqueous, alcoholic, or hydroalcoholic solutions, creams, gels, emulsions, powders, or, in the presence of propellants, aerosols. Its PH value is generally between 2 and 11. Suitable adjuvants that can be used in these compositions include nonionic, anionic, cationic and zwitterionic surfactants, animal, mineral, Vegetable or synthetic oils and waxes, fatty alcohols, anionic, cationic, nonionic and zwitterionic resins commonly used in cosmetics, emulsifiers, filtering agents, organic solvents, thickeners,
Opacifiers, preservatives, sequestering agents, antioxidants, fragrances, pearlescent agents, dyes, pigments, PH regulators,
reducing agents, oxidizing agents, natural substances, protein derivatives,
Included are anti-seborrhea agents, anti-dandruff agents, hair conditioners, or active substances effective for the treatment, care or protection of the skin or hair. These compositions are in particular shampoos, rinsing lotions for use before or after hair dyeing, bleaching or perming, hair styling or conditioning lotions, treatment lotions (e.g. anti-seborrhea and anti-dandruff lotions), brushing. - Used as lotion, hair lacquer, setting lotion and perm composition. Special mention is made of the following cosmetic compositions for hair. (a) Treatment compositions or pre- or post-hair treatment compositions. This composition is suitably applied to the hair, for example, 1 to 30 minutes after rinsing. These various treatment compositions are
Various adjuvants, in particular polyethylene glycol and its derivatives, anionic, cationic, zwitterionic and nonionic resins customary in hair compositions, pH regulators, protein derivatives (e.g. optionally quaternized) natural substances (e.g. plant extracts), fatty alcohols (e.g. cetyl, stearyl, cetylstearyl and oleyl alcohol), optionally polyethoxylated or polyglycerolated alcohols,
Animal, vegetable, mineral or synthetic oils and waxes such as petrolatum oil (liquid petroleum), corn oil, malt oil, olive oil, soybean oil, castor oil and avocado oil (these oils and waxes may optionally contain oxyethylene). anti-seborrheic agents, anti-dandruff agents, hair styling agents (for example methylolated derivatives) as well as other cosmetic auxiliaries customary in hair cosmetic compositions. (b) A shampoo containing at least one anionic, nonionic or zwitterionic surfactant or a mixture thereof and a compound of formula () in an aqueous medium. These compositions may also contain the various adjuvants customary in such compositions, such as cationic surfactants, dyes (in the case of hair dye shampoos), preservatives, thickeners, foam stabilizers, foam synergists, It can also contain emollients, sequestrants, cosmetic resins, fragrances, protein derivatives, natural substances and oils, and all other auxiliaries used in shampoos. The concentration of detergent in these shampoos is generally between 2 and 50% by weight.
It is. Among non-ionic detergents, mono-alcohols, α-diols, alkylphenols,
Condensation products of amides or diglycolamides with glycerol (e.g. FR 1477048,
2091516 and 2328763, U.S. Pat.
No. 3578719, No. 3821372, No. 3928224 and
non-ionic surfactants as described in USSN 735,216), and polyethoxylated or polyglycerolated alcohols, alkylphenols, or linear chains of 8 to 18 carbon atoms and generally 2
fatty acids containing from 30 mol of ethylene oxide, ethylene oxide/propylene oxide copolymers, condensates of ethylene or propylene oxide with fatty alcohols, polyethoxylated fatty amides, polyethoxylated fatty amines, ethanolamide, glycol esters of fatty acids,
Special mention may be made of sorbitol esters of fatty acids and sutucarose esters of fatty acids. Anionic surfactants suitable for use (optionally in combination with nonionic surfactants) include, inter alia, the alkaline, ammonium, amine or amino-alcohol salts of the following compounds: Alkyl sulfates, alkyl ether sulfates, alkylamido sulfates and alkyl-amide ether sulfates, alkylaryl polyether sulfonates, monoglyceride sulfates, alkyl sulfonates, alkyl-amide sulfonates, alkylaryl sulfonates, α-olefin sulfates, Alkyl sulfosuccinate, alkyl ether sulfosuccinate, alkyl-
Amido-sulfo-succinate, alkyl-sulfo-succinamate, alkyl-sulfo-acetate, alkyl polyglycerol carboxylate, alkyl phosphate, alkyl ether phosphate, alkyl sarcosinate,
Alkyl polypeptidates, alkyl amide polypeptides, alkyl isethionates and alkyl taurates. The alkyl groups in all these compounds are generally
It has a straight chain of 12 to 20 carbon atoms. Other compounds include fatty acids (eg, oleic acid, ricinoleic acid, palmitic acid, stearic acid, copra oil, hydrogenated copra oil acid) and polyglycol ether carboxylic acids represented by the formula: Alk-( _OCH2 -CH) _o - _OCH2 - _CO2H In the formula, Alk represents a straight chain having 12 to 18 carbon atoms, and n is an integer of 5 to 15. Of course, other anionic detergents can also be used. Representative examples of amphoteric surfactants that can be used include alkylaminobetaines, mono- and di-propionates (e.g. N-alkylbetaines, N-alkylsulfobetaines, N-alkylamidobetaines), cycloimide derivatives (e.g. alkylimidazolines) and Contains asparagine derivatives. The alkyl groups in these surfactants preferably have 1 to 22 carbon atoms. Suitable foam stabilizers include fatty amides (particularly mono- and di-ethanolamides of copra fatty acids, mono- and diethanolamides of lauric and oleic acids), generally used in amounts ranging from 1 to 10% by weight of the composition. (preferably 1 to 3)% by weight. Suitable thickening agents include acrylic polymers and cellulose derivatives such as carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose. The content of thickeners is generally from 0.1 to 5% by weight. (c) Composition for hair dyeing. In particular, an oxidative dye precursor (e.g. of the ortho or para type, optionally accompanied by one or more color formers) is contained in the basic medium;
Oxidative dye compositions preferably have a pH of 8 to 11 and/or contain one or more leuco derivatives of indamines, indoanilines and indophenols and direct dyes well known in the art, or direct dyes, e.g. Direct or semi-permanent dye compositions containing nitrobenzene, azo or anthraquinone dyes and indamines, indoanilines and indophenols. (d) at least one decolorizing agent (e.g. a solution of hydrogen peroxide or other peroxides or peracids such as persulfates, perborates or percarboxylates);
and at least one compound of formula (), which may be provided in the form of powders, solutions, emulsions or gelling liquids as well as creams. These compositions generally include an alkaline agent (eg ammonia). These decolorizing compositions can be used in conventional manner. (e) Perming compositions or hair fixing compositions. The formulation of reducing and oxidizing (fixing) compositions is well known, and some of the fundamental works in the beauty world [e.g.
"Capillaires" Paris, 1966 (Gauthier-
Villard)”. In the perming method according to the present invention, one of two compositions is used.
contains a compound of formula (). The reducing composition also includes a reducing agent as well as adjuvants which enable the composition to be in the form of a powder that can be dispersed in lotions or liquid vehicles, optionally with a compound of formula (). The PH value of the composition is generally from 7 to
It is 10. The reducing agent is most often a mercaptan (eg thioglycerol or thioglycolic acid or derivatives thereof). The composition according to the invention can also be applied to the skin in one of the different forms mentioned above. This composition gives a soft feel to the skin. These compositions contain, together with one or more compounds of formula (), cosmetic adjuvants commonly used on the skin, in particular perfumes,
dyes, pigments, preservatives, sequestrants, emulsifiers, thickeners and filtering agents). These compositions especially take the form of creams and lotions for the hands and face, sunscreen creams, coloring creams, make-up remover emulsions, shaving creams, bath oils or foaming liquids, deodorizing compositions, All of these can be manufactured using conventional methods. The invention also provides a method of care comprising applying to the hair, skin or nails a sufficient amount of the composition of the invention. The invention is further illustrated by the following examples. In the example, x represents an integer from 3 to 10. Example 1 Preparation of a mixture of intermediates represented by the following formula. 169 g (0.8 mol) of acetic ester of undecylenyl alcohol, 102 g (0.88 mol) of methyldichlorosilane and 0.5 ml of hexachloroplatinic acid in a 2% strength methanol solution are placed in one autoclave. Heat the mixture to 120°C for 5 hours. Filter the reaction mixture over a glass frit. Next, the unreacted methyl dichlorocyanate was distilled under reduced pressure, and then the dichloro derivative was distilled at 150°C.
Distill under reduced pressure of 0.5 mmHg. Add 750 ml of tetrahydrofuran and a solution of 56 g (1 mole) of potassium hydroxide in 200 ml of water. Cool the mixture to +5°C in an ice bath. A solution of the dichloro derivative in 750 ml of tetrahydrofuran is then added at a temperature of 5° C. to 10° C. (duration of addition: 1 hour 40 minutes). After stirring for a further 30 minutes, the tetrahydrofuran was removed under reduced pressure and the organic layer was collected by decantation and then dried over dry sodium sulfate at a temperature of 285°C under a pressure of 10 ^-3 mmHg. Purify by molecular distillation. 95 g of the compound thus obtained are dissolved in 500 ml of 96° strength ethanol. Then 40 g of sodium hydroxide solution with a content of 10 meq/g are added under reflux. After heating for 1 hour and 30 minutes, the alcohol is removed under reduced pressure. The residue is taken up in 100 ml water and 200 ml ether. Separate the organic layer by decantation and dry over sodium sulfate. 78 g of product are thus obtained. The product is waxy and characterized using gas phase chromatography and infrared spectroscopy.
Its pour point is 52°C. Example 2 Preparation of an intermediate mixture represented by the following formula. In the formula, R ₅ represents a CH ₂ Cl group. 9.2 g of intermediate prepared according to Example 1 (
Dissolve a) in 70 ml of benzene. Then add 4 g (0.02 mol) of triethylamine followed by 9.5 g (0.08 mol) in 40 ml of benzene.
of thionyl chloride is added over 30 minutes at ambient temperature. After heating under reflux for 5 hours, triethylamine hydrochloride was filtered off and diluted with 10 ml of benzene.
Rinse thoroughly. The filtrate is evaporated to dryness under reduced pressure. 9.5 g of compound are thus obtained. This compound is a black oil. Organic chlorine: 4.71 meq/g. Example 3 Preparation of a mixture of compounds represented by the following formula. 1st step: Preparation of methylene ester 99 g (0.5 mol) of methyl undecylenate,
A mixture of 63.5 g (0.55 mol) of methyldichlorosilane and 0.5 ml of a 2% strength methanol solution of hexachloroplatinic acid is heated to 120° C. for 5 hours in an autoclave. After filtration, the remaining reactants were distilled off under reduced pressure,
Next, 98g of dichloro derivative was added under a pressure of 2mmHg.
Distill at a temperature of 155°C to 160°C. 500ml of tetrahydrofuran in 130ml of water
Add to a solution of 36g KOH. Then 98 g (0.32 mol) of the dichloro derivative in 500 ml of tetrahydrofuran are added at a temperature of 5° C. to 10° C. (reaction period: 1 hour 30 minutes). After removing the tetrahydrofuran, the organic layer is separated by decantation, dried over sodium sulphate and then purified by molecular distillation at a temperature of 285°C. The oil thus obtained (saponification value 3.85 milliequivalent/
g) is investigated using gas phase chromatography and infrared spectroscopy. 2nd stage: Saponification of the ester 52 g of the product thus obtained are dissolved in 200 ml of 96° strength ethanol and then 24 g of a 40% strength aqueous solution of sodium hydroxide and 70 ml of water are dissolved under reflux. Add. After heating for 30 minutes, the alcohol was removed under reduced pressure and the residue was absorbed into 170 ml of water, then 55 ml
Acidify this mixture using 6N hydrochloric acid. The desired acid is filtered off, washed with water and dried. The solid product thus obtained (melting point 40° C., acid number 4 meq/g) is soluble in water in the presence of a base (eg sodium hydroxide or triethanolamine). Example 4 Production of a mixture of compounds represented by the following formula 3.2 g (40 meq.) of methylethanolamine are added to a solution of 4.5 g (20 meq. of chlorine) of the intermediate chloro derivative () prepared according to Example 2 in 25 ml of toluene. After heating under reflux for 10 hours, the reaction mixture is cooled and then a solution of 4 g of sodium methylate in methanol (content 5 meq/g) is added at ambient temperature. After stirring for 1/2 hour, the sodium chloride formed is filtered off and the solvent is removed under reduced pressure. The product thus obtained is oily and soluble in water in the presence of mineral or organic acids. Alkali value: 3.58 meq/g. Example 5 Preparation of a mixture of compounds of the formula: 5.1g (50 milliequivalents of primary amine group) of N,N
-dimethylaminopropylamine in the first step of Example 3.
10 g (40 meq. of methyl ester of formula (), where R is _CH3 ) obtained according to the steps
Add to. After heating to 100° C. for 6 hours under nitrogen atmosphere, excess amine is distilled off under reduced pressure. The remaining product is a brown oil and is soluble in water in the presence of mineral or organic acids. Alkali value: 2.7 meq/g. Tertiary amine value: 2.5 meq/g. Example 6 Preparation of a mixture of compounds of the formula: 2.3 g (19.2 meq.) of ethyl thioglycolate were added at 50° C. to a solution of 3.85 g (19.2 meq.) of the intermediate () prepared according to Example 2 in 40 ml of isopropanol and then A solution of 4.8 g of sodium methylate in methanol (content 4 meq/g) is added dropwise to the solution. The reaction mixture is heated under reflux for 10 hours. After filtering off the sodium chloride formed, 20 ml of 96° strength ethanol, 5
Add ml of water and 1.55 g of aqueous sodium hydroxide solution (content 10 meq/g). After heating under reflux for 1 hour, the solvent is removed under reduced pressure, then the residue is taken up in 50 ml of water and the mixture is washed twice with 10 ml of chloroform. Acidify this aqueous solution using 10 ml of 2N hydrochloric acid,
Next, extract three times with 10 ml of chloroform. Dry the organic layer over sodium sulfate and then concentrate to dryness. The resulting product is waxy and soluble in water in the presence of a base (eg sodium hydroxide or triethanolamine). Acid value: 2.9 meq/g. Example 7 Preparation of a mixture of compounds of the formula: 5.5 g (hydroxyl group 23.5
(milliequivalents) of intermediate (a) are dissolved in 10 ml of chloroform. Next, 2.72 g (23.5 meq) of chlorosulfonic acid in 5 ml of chloroform are added, while maintaining the temperature at 20°C to 25°C. After stirring for 30 minutes,
The solvent is removed under reduced pressure and the residue is taken up in 25 ml of absolute ethanol. 4.7 g of sodium methylate in methanol (content 5 meq/g)
to neutralize the acid. Filter off the sodium salts, rinse with absolute ethanol and dry. A white solid (slightly opalescent when dissolved in water) is thus obtained. Elemental analysis: C% H% S% 40.04 7.38 8.30 40.21 7.04 8.44 Example 8 Preparation of a mixture of compounds represented by the following formula. 0.18ml of boron trifluoride/ether complex,
9.8 g of compound (a) prepared according to Example 1
and then add 25.9 g (200 meq.) of tertiary butyl glycidyl ether at 50°C. After heating to 70°C for 2 hours, 0.35g of sulfoacetic acid is added and the mixture is gradually heated to 90°C over a period of 3 hours. Add 5 ml of water and bring the mixture from 100°C to 105°C for 4
Heat for an hour. After cooling, the reaction mixture was absorbed into 300 ml of water and mixed with 40 g of ion exchange resin (Amberlite).
Neutralize the catalyst in the presence of MB1). The resin is then filtered off and rinsed twice with 50 ml of water. After evaporation to dryness, an opalescent paste is obtained when dissolved in water. Hydroxyl number: 8.6 meq/g. Example 9 Preparation of a mixture of compounds of the formula: 0.24 ml of boron trifluoride ethylate was added to 8 g (35 meq.) of compound (a) prepared according to Example 1, followed by 22.7 g (175 meq.) of tert-butyl glycidyl ether and 16.3 g. (175 meq.) epichlorohydrin at 70 °C.
Add over 1 1/2 hours. After heating for 4 hours, 0.45 g of sulfoacetic acid is added and the mixture is heated to 90° C. for 3 hours. After adding 2 ml of water, the mixture was boiled for a further 1 hour and 30 minutes at 105
Heat to ℃. 12 g (100 meq) of ethyl thioglycolate in 50 ml of absolute ethanol (19.6 g (chlorine)
100 meq) of the compound thus obtained at a temperature of 40°C, then 25 g (100 meq)
of sodium methylate drop by drop. After heating under reflux for 2 hours, the sodium chloride is filtered off and the solution is then removed under reduced pressure. 60ml of residue
of 96° strength ethanol and 9.3 g of sodium hydroxide solution (content 10 meq/g) are added to this. 40 ml of water are added and the mixture is heated under reflux for 1 hour. Then add 25ml of 3N hydrochloric acid. The product is salted out, washed four times with 30 ml of water and then dried.
The brown wax thus obtained is prepared using a base (e.g. sodium hydroxide or triethanolamine).
Soluble in water in the presence of. Acid value: 3.4 meq/g. Example 10 The following hair dye composition is manufactured. Triethanolamine salt of the compound of Example 3 1.2 g 1,4-di(methylamino)-2-nitrobenzene 0.07 g Water Enough to make 100 g This solution is applied to bleached hair for 20 minutes. After rinsing, shampooing, and rinsing again, it imparts a pale pink cyclamen-like color. Example 11 The following hair dye composition is manufactured. Triethanolamine salt of the compound of Example 6 1 g 4-N-(β-hydroxyethyl)amino-4-
Phenyl-Azo-Nitro-Phenol 0.08g Water Enough to make 100g Apply this solution to bleached hair for 30 minutes. After rinsing, shampooing, and rinsing again, it gives a pink shampoo-like color. Example 12 The following colored setting lotion is manufactured. 1 g of triethanolamine salt of the compound of Example 6 2 g of vinylpyrrolidone/vinyl acetate (60/40) copolymer 0.1 g of nitroparaphenylenediamine 100 g of water and enough to make this colored setting lotion applied to bleached hair. , imparts a salmon-colored hue to the hair. Example 13 The following hair dye composition is manufactured. Triethanolamine salt of the compound of Example 3 1.2 g para-toluylene diamine hydrochloride 0.24 g para-aminophenol 0.1 g 2-methyl-5-[N-(β-hydroxyethyl)
Amino]phenol 0.15 g 1-methoxy3-nitro-4-[N-(β-hydroxyethyl)amino]benzene 0.2 g Cetyl alcohol 18 g 20% ammonium lauryl sulfate 12 g Cetyl oxyethylated with 13 moles of ethylene oxide Stearyl alcohol 3g Lauryl alcohol 5g 22゜Ammonia 13cm ^3Sodium salt of diethylenetriaminepentaacetic acid
3 g water Enough to make 100 g At the point of use, a mixture of the resulting cream and an equal amount of 6% hydrogen peroxide is applied to the bleached hair. After 30 minutes, rinse and shampoo, rinse again and dry, leaving your hair with a rosewood hue. Example 14 The following anionic shampoo is manufactured. Triethanolamine salt of the compound of Example 3 1 g Triethanolamine lauryl sulfate 7 g Lauryl diethanolamide 1.5 g Hydrochloric acid Sufficient amount to make PH7.5 Water Sufficient amount to make 100 g Example 15 The following nonionic shampoo is prepared. . Compound of Example 7 0.8g Hydroxyalkyl ether of polyglycerol represented by the following formula 7g R-CHOH- _CH2 -O[ _-CH2 -CHOH- _CH2-
O] - _3.5 H (where R represents a mixture of alkyl groups having 9 to 12 carbon atoms) Diethanolamide of copra fatty acid 3g Hydrochloric acid Enough amount to make PH7.3 Water Sufficient amount to make 100g Example 14 Apply the shampoo of 15 to the pre-moistened hair head to emulsify all the dust. Rinse your hair and apply this shampoo again to get a rich lather. The hair is soft after rinsing and stays set well after being rolled with a setting roller. Example 16 This example is similar to Example 11, but instead of 1 g of the compound of Example 6 it contains 1 g of the triethanolamine salt of the compound of Example 9. Example 17 This example is similar to Example 10, but contains 1.2 g of the compound of Example 8 instead of 1.2 g of the triethanolamine salt of the compound of Example 3. Example 18 This example is similar to Example 15, but with 0.8
0.5 g of the compound of example 4 and 0.5 g of the compound of example 5 are contained instead of g.

Claims (1)

[Claims] 1. General formula (In the formula, x is an integer from 3 to 10, and A is the formula: (a) (However, R ₁ is [-CH ₂ -CH ₂ -O]- _o H,
n is an integer from 1 to 10, and u is 0 or 1), (b) (However, V is an anion of an organic or inorganic acid, R ₁ is as defined in (a), and u is 0 or 1), (c) -CONH-(CH ₂ ) _n - B (where m is 2 or 3, B represents a group [formula] or [formula] (u is 0 or 1, and V is an anion of an organic acid or inorganic acid)), (d) (However, u and w are the same or different and are 0 or 1, M represents a hydrogen atom, an ammonium group, or an alkali metal), (e) CH ₂ -O-SO ₃ M (However, M is (d) ), (f) (However, p and q may be the same or different and indicate a positive number up to 0 or 10, but both p and q are not 0.
Y represents hydroxypropylene group, Z represents OH
or [Formula] (where u is 0 or 1, and M represents a hydrogen atom, an ammonium group, or an alkali metal)) A hair treatment containing at least 0.5×10 ^-2 g/ Composition for use.